CN105440268A - Aliphatic-aromatic-polylactic acid multiblock copolymer - Google Patents
Aliphatic-aromatic-polylactic acid multiblock copolymer Download PDFInfo
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Abstract
The invention provides an aliphatic-aromatic-polylactic acid multiblock copolymer. The aliphatic-aromatic-polylactic acid multiblock copolymer is prepared through carrying out an esterification reaction and a condensation polymerization reaction on bishydroxyl-terminated polylactic acid, an aromatic dicarboxylic acid compound, an aliphatic dicarboxylic acid compound and a dihydric alcohol compound. The aliphatic-aromatic-polylactic acid multiblock copolymer includes an aliphatic-aromatic chain segment, so the flexibility of the aliphatic-aromatic-polylactic acid multiblock copolymer is improved. An experiment result shows that the elongation at break of the aliphatic-aromatic-polylactic acid multiblock copolymer is 210-600%. A preparation method of the aliphatic-aromatic-polylactic acid multiblock copolymer has the advantages of simple process, mild reaction conditions, industrial production benefiting, and reduction of pollution to environment due to no use of a chain extender in the whole preparation process.
Description
Technical field
The invention belongs to technical field of polymer, particularly relate to a kind of aliphatic-aromatic-poly(lactic acid) segmented copolymer.
Background technology
Along with the aggravation of environmental pollution, people propose higher requirement for the use of macromolecular material, while meeting materials'use performance, require macromolecular material environmentally safe.Poly(lactic acid) is based on biomass resource and degradable Green Polymer Material, nontoxic, nonirritant, there is the advantages such as good biocompatibility, Bioabsorbable, but containing a large amount of ester bonds in poly(lactic acid), wetting ability is poor, reduce the biocompatibility of poly(lactic acid) and other material, poly(lactic acid) is originally as simple linear polymer, and melt strength is low, and fragility is high, shock resistance is poor, limits it and widely uses.
For the above-mentioned shortcoming of poly(lactic acid), many researchers have carried out large quantity research to the modification of poly(lactic acid) in recent years.Publication number is that the Chinese patent of CN102977319A discloses a kind of degradable poly lactic acid di-block copolymer, its preparation method and the application in polydactyl acid thereof.Under inert atmosphere protection, the poly(lactic acid) being hydroxyl by end group that is dry, that dewater adds in reaction unit; Add vulcabond again, stir at being heated to 185 DEG C ~ 190 DEG C and carry out reaction 5h ~ 8h; Add containing hydroxyl, degradable polymer again, stir at 185 DEG C ~ 190 DEG C and carry out reaction 1h ~ 2h; Add diisocyanate in the most backward reaction unit, stir and react at 185 DEG C ~ 190 DEG C, reaction can obtain degradable poly lactic acid di-block copolymer to being difficult to stirring.This degradable poly lactic acid di-block copolymer and polylactic resin consistency good, but its mechanical property is poor, and elongation at break can only reach 60%.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of aliphatic-aromatic-poly(lactic acid) segmented copolymer, aliphatic-aromatic provided by the invention-poly(lactic acid) segmented copolymer has good snappiness.
The invention provides a kind of aliphatic-aromatic-poly(lactic acid) segmented copolymer, obtained by following preparation method:
Two hydroxyl-terminated polylactic acid, aromatic binary carboxylic acid compounds, aliphatic dicarboxylic acid compounds and dibastic alcohol compound are carried out esterification and polycondensation, obtains aliphatic-aromatic-poly(lactic acid) segmented copolymer.
Preferably, the number average mol weight of described pair of hydroxyl-terminated polylactic acid is 0.9kg/mol ~ 7.5kg/mol.
Preferably, described aromatic binary carboxylic acid compounds comprises one or more in the two alkyl ester of phthalic acid, naphthalic acid, phenylate dioctyl phthalate, aromatic diacid acid anhydride, aromatic binary carboxylic acid mono alkyl ester and aromatic binary carboxylic acid.
Preferably, described dibastic alcohol compound is one or more in the dibastic alcohol compound of C2 ~ C50;
Described aliphatic dicarboxylic acid compounds is one or more in the aliphatic dicarboxylic acid compounds of C2 ~ C40.
Preferably, the temperature of described esterification is 150 DEG C ~ 230 DEG C;
The time of described esterification is 1h ~ 10h.
Preferably, the temperature of described polycondensation is 210 DEG C ~ 280 DEG C;
The time of described polycondensation is preferably 2h ~ 48h;
The pressure of described polycondensation is 50Pa ~ 2000Pa.
Preferably, total amount of substance of described aliphatic dicarboxylic acid compounds and aromatic binary carboxylic acid compounds is 1:1 ~ 1:2 with total amount of substance ratio of described dibastic alcohol compound and two hydroxyl-terminated polylactic acid;
The amount of substance of described aromatic binary carboxylic acid compounds and described aliphatic dicarboxylic acid compounds is than being 10:90 ~ 90:10;
The mass ratio of described dibastic alcohol compound and described pair of hydroxyl-terminated polylactic acid is 10:90 ~ 90:10.
Present invention also offers aliphatic-aromatic described in a kind of technique scheme-poly(lactic acid) segmented copolymer, there is structure shown in formula I:
In formula I, described R
1be selected from alkylene or-R
5-O-R
6, described R
5and R
6independently selected from alkylene;
Described R
2be selected from alkylene;
Described R
3be selected from alkylene or-R
7-O-R
8, described R
7and R
8independently selected from alkylene;
Described R
4be selected from aromatic base or-R
9-O-R
10, described R
9and R
10independently selected from aromatic base;
Described m=6 ~ 50, n=5 ~ 500, p=1 ~ 50, q=1 ~ 50, s=5 ~ 500.
Preferably, described m=10 ~ 40, n=50 ~ 400, p=10 ~ 40, q=10 ~ 40, s=50 ~ 400.
Preferably, described R
1be selected from alkylene or the-R of C2 ~ C50
5-O-R
6, described R
5and R
6independently selected from C2 ~ C25 alkylene;
Described R
2be selected from the alkylene of C2 ~ C40;
Described R
3be selected from alkylene or the-R of C2 ~ C50
7-O-R
8, described R
7and R
8independently selected from C2 ~ C25 alkylene.
The invention provides a kind of aliphatic-aromatic-poly(lactic acid) segmented copolymer, obtained by following preparation method: two hydroxyl-terminated polylactic acid, aromatic binary carboxylic acid compounds, aliphatic dicarboxylic acid compounds and dibastic alcohol compound are carried out esterification and polycondensation, obtain aliphatic-aromatic-poly(lactic acid) segmented copolymer.Aliphatic-aromatic provided by the invention-poly(lactic acid) segmented copolymer comprises aliphatic-aromatic segment, improves the snappiness of aliphatic-aromatic-poly(lactic acid) segmented copolymer.Experimental result shows: the elongation at break of aliphatic-aromatic provided by the invention-poly(lactic acid) segmented copolymer is 210% ~ 600%.
In addition, aliphatic-aromatic-poly(lactic acid) segmented copolymer preparation method technique is simple, and reaction conditions is gentle, is beneficial to suitability for industrialized production; Do not use chainextender in whole preparation process, decrease the pollution to environment.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer that the embodiment of the present invention 1 obtains;
Fig. 2 is the stress-strain curve of poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer that poly(lactic acid) and the embodiment of the present invention 1 obtain.
Embodiment
The invention provides a kind of aliphatic-aromatic-poly(lactic acid) segmented copolymer, obtained by following preparation method:
Two hydroxyl-terminated polylactic acid, aromatic binary carboxylic acid compounds, aliphatic dicarboxylic acid compounds and dibastic alcohol compound are carried out esterification and polycondensation, obtains aliphatic-aromatic-poly(lactic acid) segmented copolymer.Aliphatic-aromatic provided by the invention-poly(lactic acid) segmented copolymer comprises aliphatic-aromatic segment, improves the snappiness of aliphatic-aromatic-poly(lactic acid) segmented copolymer.Experimental result shows: the elongation at break of aliphatic-aromatic provided by the invention-poly(lactic acid) segmented copolymer is 210% ~ 600%.
The order by merging of the present invention to described pair of hydroxyl-terminated polylactic acid, aromatic binary carboxylic acid compounds, aliphatic dicarboxylic acid compounds and dibastic alcohol compound does not have special restriction, preferably described pair of hydroxyl-terminated polylactic acid and aromatic binary carboxylic acid compounds are first mixed, then add aliphatic dicarboxylic acid compounds and dibastic alcohol compound successively wherein.
The source of the present invention to described pair of hydroxyl-terminated polylactic acid does not have special restriction, adopt well known to those skilled in the art pair of hydroxyl-terminated polylactic acid, as its commercial goods can be adopted, the technical scheme of the two hydroxyl-terminated polylactic acid of preparation well known to those skilled in the art also can be adopted to prepare voluntarily.In the present invention, the preparation method of described pair of hydroxyl-terminated polylactic acid preferably includes following steps:
Under oxygen-free environment, dibastic alcohol compound and rac-Lactide are carried out polyreaction, obtain two hydroxyl-terminated polylactic acid.
The present invention is preferably airtight and in oxygen-free environment, described dibastic alcohol compound and rac-Lactide are carried out polyreaction.The present invention realizes oxygen-free environment preferably by nitrogen or rare gas element; Described rare gas element is preferably argon gas.The order by merging of the present invention to described dibastic alcohol compound and rac-Lactide does not have special restriction, in a particular embodiment, is preferably joined in rac-Lactide by described dibastic alcohol compound.The present invention preferably carries out polyreaction under the condition stirred.
The container of the present invention to described polyreaction does not have special restriction, can be reactor well known to those skilled in the art, and in an embodiment of the present invention, described reactor can be specially reactor or the flask of band two ventage.
The present invention carries out to be beneficial to reaction, preferably described dibastic alcohol compound and rac-Lactide is carried out polyreaction in the presence of a catalyst.Described dibastic alcohol compound and rac-Lactide, in order to distinguish catalyzer described in following technical proposals, are carried out catalyzer called after first catalyzer that polyreaction is used by the present invention.The order of the present invention to described dibastic alcohol compound, rac-Lactide and the first catalyst mix does not have special restriction, in a particular embodiment, described dibastic alcohol compound and rac-Lactide first can be mixed, then add the first catalyzer wherein.In the present invention, described first catalyzer preferably include in aluminum isopropylate, divinyl zinc, tin protochloride and stannous octoate one or more, more preferably comprise in stannous octoate and aluminum isopropylate one or both; The mass ratio of described first catalyzer and rac-Lactide is preferably (0.01 ~ 1): 100, is more preferably (0.05 ~ 0.9): 100, most preferably is (0.1 ~ 0.5): 100.
In the present invention, described dibastic alcohol compound as while polyreaction raw material, also as the initiator of polyreaction.In the present invention, described dibastic alcohol compound can be straight dihydric alcohol compounds, and can be branched chain dihydric alcohol compound, the present invention have special restriction to this yet, described dibastic alcohol compound be preferably in the dibastic alcohol compound of C2 ~ C50 one or more, be more preferably ethylene glycol, propylene glycol, BDO, 1,3 butylene glycol, 1,2-butyleneglycol, 2,3-butanediol, 1,5-PD, Isosorbide-5-Nitrae-two amylalcohol, 1,3-pentanediol, 1,2-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2,2,4-trimethylammonium-1,3-pentanediol, 1,6-hexylene glycol, 1,5-hexylene glycol, Isosorbide-5-Nitrae-hexylene glycol, 1,3-hexylene glycol, 1,2-hexylene glycol, 2,5-hexylene glycol, 2-ethyl-1,3-hexylene glycol, 2,5-dimethyl-2,5-hexylene glycol, phenyl-1，2-ethandiol, Diethylene Glycol, triethylene glycol, Tetraglycol 99, dipropylene glycol, tripropylene glycol, 1,2-ring pentanediol, 1,3-ring pentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, Isosorbide-5-Nitrae-cyclohexanediol, the two methylol hexanaphthene of 1,2-, the two methylol hexanaphthene of 1,3-, Isosorbide-5-Nitrae-bis-methylol hexanaphthene, 3-methoxyl group-1,2-PD, 1,7-heptanediol, 1,2-heptanediol, 1,8-ethohexadiol, 1,2-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, 1,2-decanediol, 1,11-undecane, 1,2-dodecanediol, 1,12-dodecanediol, 1,13-tridecane diols, 1,14-tetradecane diols, 1,15-pentadecane diols, 1,16-hexadecane diol, 1,17-heptadecane diols, 1,18-octadecandiol, one or more in 1,19-nonadecane glycol and 1,20-icosane diols, most preferably comprise ethylene glycol, dipropylene glycol, Diethylene Glycol, BDO, 1,3 butylene glycol, 1,2-butyleneglycol, 2,3-butanediol, one or more in hexylene glycol and Isosorbide-5-Nitrae-cyclohexanediol.
In the present invention, described rac-Lactide comprises one or more in L-rac-Lactide, DL-rac-Lactide and meso-rac-Lactide.In the present invention, the mol ratio of described dibastic alcohol compound and rac-Lactide is preferably 1:7 ~ 50, is more preferably 1:10 ~ 40, most preferably is 1:15 ~ 30.
In the present invention, the temperature of described polyreaction is preferably 110 DEG C ~ 180 DEG C, is more preferably 120 DEG C ~ 170 DEG C, most preferably is 130 DEG C ~ 160 DEG C; The time of described polyreaction is preferably 3h ~ 50h, is more preferably 8h ~ 40h, most preferably is 12h ~ 30h, is the most preferably 14h ~ 20h.The type of heating of the present invention to the temperature reaching described polyreaction does not have special restriction, preferably adopts oil bath to heat.
The present invention, preferably after described polyreaction terminates, heats up to vacuumize and removes unreacted monomer, obtain two hydroxyl-terminated polylactic acid.In the present invention, the temperature of described intensification is preferably 140 DEG C ~ 200 DEG C, is more preferably 150 DEG C ~ 180 DEG C; The described pressure vacuumized is preferably 180Pa ~ 1500Pa, is more preferably 200Pa ~ 1000Pa.
Particularly, the present invention carries out polyreaction with 1,3-pentanediol and rac-Lactide, obtains having two hydroxyl-terminated polylactic acids of structure shown in formula II:
In formula II, described m1=6 ~ 50.
The present invention carries out gel osmoticing chromatogram analysis to the two hydroxyl-terminated polylactic acids obtained, detailed process is as follows: be dissolved in 5mL chloroform by two for 5mg hydroxyl-terminated polylactic acid and dissolve, meter sample device is injected with microsyringe sample thief 100 μ L after filtering, etc. test to be done, condition determination is: chloroform is moving phase, flow velocity is 1mL/min, does universal calibration with the polystyrene standards of monodispersity.
Test result shows: the number average mol weight of the two hydroxyl-terminated polylactic acids obtained is 0.9kg/mol ~ 7.5kg/mol.
In the present invention, described aromatic binary carboxylic acid compounds comprises one or more in aromatic binary carboxylic acid compound and aromatic binary carboxylic acid analog derivative; Described aromatic binary carboxylic acid compounds can be linear aromatic di-carboxylic acid compounds, and can be branched aromatic di-carboxylic acid compounds, the present invention have special restriction to this yet.In the present invention, described aromatic binary carboxylic acid compounds preferably includes one or more in the two alkyl ester of phthalic acid, naphthalic acid, phenylate dioctyl phthalate, aromatic diacid acid anhydride, aromatic binary carboxylic acid mono alkyl ester and aromatic binary carboxylic acid, wherein, the two alkyl esters in the two alkyl ester of described aromatic binary carboxylic acid preferably include in dimethyl ester, diethyl ester, two-propyl diester, di-n-butyl ester, two-tertiary butyl ester, Di-Isobutyl ester, two-n-octyl ester, two-isooctyl acrylate, list-2-(ethyl hexyl) ester, two-2-(ethyl hexyl) esters, two-n-nonyl ester, two-different nonyl ester, two positive decyl ester, two-n-undecane base ester, diiso decyl ester and two different undecyl esters one or more, described aromatic binary carboxylic acid compounds most preferably comprises terephthalic acid, m-phthalic acid, phthalic acid, dimethyl terephthalate (DMT), diethyl terephthalate, dibutyl terephthalate, 2, 6-naphthalic acid, 2, 6-naphthalene diformic acid dimethyl ester, 2, 7-naphthalic acid, 2, 7-naphthalene diformic acid dimethyl ester, 3, 4'-oxydibenzoic acid, 2, 4'-oxydibenzoic acid dimethyl ester, 4, 4'-oxydibenzoic acid, 4, 4'-oxydibenzoic acid dimethyl ester, 1, 4'-naphthalic acid and 1, one or more in 4'-naphthalene diformic acid dimethyl ester, the most preferably include terephthalic acid, one or more in dimethyl terephthalate (DMT) and naphthalene dicarboxylic anhydride.
In the present invention, described aliphatic dicarboxylic acid compounds comprises one or more in aliphatic dicarboxylic acid and aliphatic dicarboxylic acid derivative; Described aliphatic dicarboxylic acid compounds can be straight-chain aliphatic di-carboxylic acid compounds, and can be branched aliphatic di-carboxylic acid compounds, the present invention have special restriction to this yet.In the present invention, described aliphatic dicarboxylic acid compounds preferably include in the aliphatic dicarboxylic acid compounds of C2 ~ C40 one or more, more preferably comprise in the two alkyl ester of aliphatic dicarboxylic acid, aliphatic diacid acid anhydride, aliphatic dicarboxylic acid mono alkyl ester and aliphatic dicarboxylic acid one or more; Wherein, the two alkyl esters in the two alkyl ester of described aliphatic dicarboxylic acid preferably include in dimethyl ester, diethyl ester, dipropyl, two-butyl ester, diamyl ester, dihexyl, two-2-(ethyl hexyl) esters, two heptyl esters, two-octyl group ester, two-nonyl ester, two-decyl ester, dibenzyl ester and two-undecyl ester, ester one or more; Described aliphatic dicarboxylic acid compounds most preferably comprise in hexanodioic acid, succinic acid, sebacic acid, Succinic anhydried, pyrovinic acid, dimethyl succinate and monomethyl succinate one or more.
In the present invention, carry out esterification and the raw material dibastic alcohol compound that polycondensation is used can with described in technique scheme, the dibastic alcohol compound that carries out polyreaction with rac-Lactide is identical, described esterification and polycondensation and described polyreaction also can adopt different types of dibastic alcohol compound, and the present invention does not have special restriction to this.In the present invention, carry out esterification consistent with the category of the dibastic alcohol compound carrying out polyreaction in technique scheme with the category of the raw material dibastic alcohol compound that polycondensation is used, repeat no more in this kind to the dibastic alcohol compound carrying out esterification and polycondensation.
In the present invention, total amount of substance of described aliphatic dicarboxylic acid compounds and aromatic binary carboxylic acid compounds is 1:1 ~ 1:2 with total amount of substance ratio of described dibastic alcohol compound and two hydroxyl-terminated polylactic acid, be more preferably 1:1.1 ~ 1:1.8, most preferably be 1:1.2 ~ 1:1.7;
The amount of substance of described aromatic binary carboxylic acid compounds and described aliphatic dicarboxylic acid compounds, than being 10:90 ~ 90:10, being more preferably 20:80 ~ 80:20, most preferably being 30:70 ~ 70:30;
The mass ratio of described dibastic alcohol compound and described pair of hydroxyl-terminated polylactic acid is 10:90 ~ 90:10, is more preferably 20:80 ~ 80:20, most preferably is 30:70 ~ 70:30.
The present invention is in order to be beneficial to esterification and polycondensation is carried out, preferably under the condition of the second catalyzer, described pair of hydroxyl-terminated polylactic acid, aromatic binary carboxylic acid compounds, aliphatic dicarboxylic acid compounds and dibastic alcohol compound are carried out esterification and polycondensation.In the present invention, described second catalyzer preferably includes the compound of titaniferous, stanniferous compound, compound containing aluminium, sulfonic compound and containing one or more in the compound of zinc, more preferably comprises one or more in zinc acetate, tetrabutyl titanate, tin protochloride, isopropyl titanate, stannous octoate and tosic acid.In the present invention, the total mass of described aliphatic dicarboxylic acid compounds and aromatic binary carboxylic acid compounds and the mass ratio of described second catalyzer are preferably 100:0.01 ~ 1, are more preferably 100:0.05 ~ 0.9, most preferably are 100:0.1 ~ 0.5.
In the present invention, described esterification and polycondensation are carried out in same system, regulate the carrying out of esterification and polycondensation by changing reaction conditions.Described pair of hydroxyl-terminated polylactic acid, dibastic alcohol compound, aliphatic dicarboxylic acid compounds and aromatic binary carboxylic acid compounds are preferably first carried out esterification by the present invention, collect the water that esterification generates, then raised temperature, vacuumize and carry out polycondensation.The present invention preferably rises to the temperature needed for esterification with the temperature rise rate of 2 DEG C/min ~ 20 DEG C/min, is more preferably 4 DEG C/min ~ 15 DEG C/min, most preferably is 6 DEG C/min ~ 10 DEG C/min.In the present invention, the temperature of described esterification is preferably 150 DEG C ~ 230 DEG C, is more preferably 160 DEG C ~ 210 DEG C, most preferably is 165 DEG C ~ 200 DEG C; The time of described esterification is preferably 1h ~ 10h, is more preferably 2h ~ 8h, most preferably is 3h ~ 7h; The temperature of described polycondensation is preferably 210 DEG C ~ 280 DEG C, is more preferably 220 DEG C ~ 270 DEG C, most preferably is 230 DEG C ~ 250 DEG C; The time of described polycondensation is preferably 2h ~ 48h, is more preferably 3h ~ 45h, most preferably is 5h ~ 30h; The pressure of described polycondensation is preferably 50Pa ~ 2000Pa, is more preferably 100Pa ~ 1500Pa, most preferably is 200Pa ~ 1000Pa.
The present invention's aliphatic-aromatic-poly(lactic acid) segmented copolymer according to technique scheme preferably has structure shown in formula I:
In formula I, described R
1be selected from alkylene or-R
5-O-R
6, described R
5and R
6independently selected from alkylene;
Described R
2be selected from alkylene;
Described R
3be selected from alkylene or-R
7-O-R
8, described R
7and R
8independently selected from alkylene;
Described R
4be selected from aromatic base or-R
9-O-R
10, described R
9and R
10independently selected from aromatic base;
Described m=6 ~ 50, n=5 ~ 500, p=1 ~ 50, q=1 ~ 50, s=5 ~ 500.
In the present invention, described m=6 ~ 50, preferred m=10 ~ 40, more preferably m=15 ~ 35;
Described n=5 ~ 500, preferred n=50 ~ 400, more preferably n=60 ~ 380;
Described p=1 ~ 50, preferred p=10 ~ 40, more preferably p=15 ~ 35;
Described q=1 ~ 50, preferred q=10 ~ 40, more preferably q=15 ~ 35;
Described s=5 ~ 500, preferred s=50 ~ 400, more preferably s=60 ~ 380.
In the present invention, described R
1be selected from alkylene or-R
5-O-R
6, described R
5and R
6independently selected from alkylene; Be preferably alkylene or the-R of C2 ~ C50
5-O-R
6, described R
5and R
6independently selected from C2 ~ C25 alkylene, be more preferably-(CH
2)
2-,-(CH
2)
4-,-(CH
2)
6-,-CH
2-CH
2-O-CH
2-CH
2-,
Described R
2be selected from alkylene, be preferably the alkylene of C2 ~ C40, be more preferably-(CH
2)
2-,-(CH
2)
4-,-(CH
2)
8-or
Described R3 is selected from alkylene or-R
7-O-R
8, described R
7and R
8independently selected from alkylene; Be preferably alkylene or the-R of C2 ~ C50
7-O-R
8, described R
7and R
8independently selected from the alkylene of C2 ~ C25; Be more preferably-(CH
2)
3,-(CH
2)
4,-(CH
2)
10,-CH
2-CH
2-O-CH
2-CH
2-or
Described R
4be selected from aromatic base or-R
9-O-R
10, described R
9and R
10independently selected from aromatic base; Be preferably
Concrete, when ethylene glycol and rac-Lactide carry out polyreaction, obtain two hydroxyl-terminated polylactic acid; Two hydroxyl-terminated polylactic acid, terephthalic acid, hexanodioic acid and butyleneglycol are carried out esterification and polycondensation, obtain having the aliphatic-aromatic-poly(lactic acid) segmented copolymer of structure shown in formula III:
In formula III, described m2=6 ~ 50, q1=1 ~ 50, p1=1 ~ 50, s1=5 ~ 500, n1=5 ~ 500.
The present invention carries out gel osmoticing chromatogram analysis to the aliphatic-aromatic with structure shown in the formula I-poly(lactic acid) segmented copolymer obtained.
Test result shows: the number-average molecular weight of the aliphatic-aromatic that the present invention obtains-poly(lactic acid) segmented copolymer is 4kg/mol ~ 140kg/mol.
The present invention carries out the test of tensile property to the aliphatic-aromatic with structure shown in the formula I-poly(lactic acid) segmented copolymer obtained, and detailed process is:
The aliphatic-aromatic of 70mm × 4mm × 1mm-poly(lactic acid) segmented copolymer is placed on Instron4456 tensile testing machine and carries out Elongation test, rate of extension is 20mm/min, probe temperature is 23 DEG C, and carries out record to the elongation at break of aliphatic-aromatic-poly(lactic acid) segmented copolymer.
Test result shows: the elongation at break of aliphatic-aromatic provided by the invention-poly(lactic acid) segmented copolymer is 210% ~ 600%.
Aliphatic-aromatic provided by the invention-poly(lactic acid) segmented copolymer is by two hydroxyl-terminated polylactic acid and aromatic binary carboxylic acid compounds, aliphatic dicarboxylic acid compounds and dibastic alcohol compound carry out esterification and polycondensation obtains, it comprises polylactic acid chain segment and aliphatic-aromatic polyester segment, improve the consistency between poly(lactic acid) and aliphatic-aromatic polyester, extend the Application Areas of poly(lactic acid).
The invention provides a kind of aliphatic-aromatic-poly(lactic acid) segmented copolymer, obtained by following preparation method: two hydroxyl-terminated polylactic acid, aromatic binary carboxylic acid compounds, aliphatic dicarboxylic acid compounds and dibastic alcohol compound are carried out esterification and polycondensation, obtain aliphatic-aromatic-poly(lactic acid) segmented copolymer.Aliphatic-aromatic provided by the invention-poly(lactic acid) segmented copolymer comprises aliphatic-aromatic segment, improves the snappiness of aliphatic-aromatic-poly(lactic acid) segmented copolymer.Experimental result shows: the elongation at break of aliphatic-aromatic provided by the invention-poly(lactic acid) segmented copolymer is 210% ~ 600%.
Two hydroxyl-terminated polylactic acid and dibastic alcohol compound, aliphatic dicarboxylic acid compounds and aromatic binary carboxylic acid compounds are carried out esterification and polycondensation by the present invention, can obtain aliphatic-aromatic-poly(lactic acid) segmented copolymer.In whole preparation process, do not use poisonous chainextender, saved cost, decrease the pollution to environment, aftertreatment is simple, makes whole technique simple, has broad application prospects and huge industrial value.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of aliphatic-aromatic-poly(lactic acid) segmented copolymer provided by the invention being described in detail, but they can not being interpreted as limiting the scope of the present invention.
Embodiment 1
The reactor of 5L with two ventages cools through repeatedly vacuumizing filling with inert gas by 1.1, then when passing into nitrogen, add rac-Lactide (1500g), butyleneglycol (130g) and stannous octoate (1g), reaction system is sealed, be placed in the oil bath being preheated to 120 DEG C, after stirring reaction 14 is little, is warming up to 180 DEG C and vacuumizes the unreacted monomer of removal, obtain two hydroxyl-terminated polylactic acid, its number average mol weight is 1kg/mol.
1.2 by above-mentioned pair of hydroxyl-terminated polylactic acid (200g), terephthalic acid (320g), hexanodioic acid (400g), butyleneglycol (520g) and tetrabutyl titanate (1g) add in flask successively, make it reach 150 degrees Celsius and stir reactant to flask heating, collect the water that reaction generates simultaneously, after 6h, temperature of reaction is set to 220 degrees Celsius, progressively raise the temperature of system, when reaching 220 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, response path is such as formula shown in a, reaction 18h, obtain poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer, its number average mol weight is 15.0kg/mol.
The present invention carries out proton nmr spectra qualification to the segmented copolymer obtained, and as shown in Figure 1, Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer that the embodiment of the present invention 1 obtains to qualification result.
In order to compare the mechanical property of the product that poly(lactic acid) and the present invention obtain, the present invention carries out stress-strain test to poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer that poly(lactic acid) and the present embodiment 1 obtain, as shown in Figure 2, Fig. 2 is the stress-strain curve of poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer that poly(lactic acid) and the embodiment of the present invention 1 obtain to test result; Wherein, curve 1 is the stress-strain curve of poly(lactic acid), and curve 2 is the stress-strain curve of poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer.As seen from Figure 2: the elongation at break of the segmented copolymer that the present embodiment obtains has had remarkable improvement than poly(lactic acid).
Embodiment 2
By hydroxyl-terminated polylactic acid (100g) two in embodiment 1.1, terephthalic acid (320g), hexanodioic acid (400g), butyleneglycol (520g) and tetrabutyl titanate (1g) add after in flask successively, flask is heated up and makes it reach 150 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 6h, temperature of reaction is set to 290 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 290 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 3h discharging, obtain poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer, its number average mol weight is 23.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 350%, has had remarkable improvement than poly(lactic acid).
Embodiment 3
Two in embodiment 1.1 hydroxyl-terminated polylactic acid (100g), terephthalic acid (320g), hexanodioic acid (400g), butyleneglycol (520g) and tetrabutyl titanate (1g) are added after in flask successively, flask is heated up and makes it reach 230 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 6h, decompression step by step is to high vacuum state, carry out polycondensation, 8h discharging, obtain poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer, its number average mol weight is 21.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 330%, has had remarkable improvement than poly(lactic acid).
Embodiment 4
The reactor of 10L with two ventages cools through repeatedly vacuumizing filling with inert gas by 4.1, then when passing into nitrogen, add rac-Lactide (1500g), decanediol (174g) and stannous octoate (1g), reaction system is sealed, put in the oil bath being preheated to 180 DEG C, stir 8 hours, obtain transparent polymkeric substance, after its reaction terminates, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain two hydroxyl-terminated polylactic acid, its number average mol weight is 1.4kg/mol;
4.2 by hydroxyl-terminated polylactic acid (150g) two in embodiment 4.1, dimethyl terephthalate (DMT) (540g), hexanodioic acid (550g), butyleneglycol (700g) and tetrabutyl titanate (1g) add after in flask successively, flask is heated up and makes it reach 230 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 4h, temperature of reaction is set to 290 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 290 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 3h discharging, obtain poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer, its number average mol weight is 22.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 550%, has had remarkable improvement than poly(lactic acid).
Embodiment 5
By hydroxyl-terminated polylactic acid (150g) two in embodiment 4.1, dimethyl terephthalate (DMT) (380g), sebacic acid (600g), butyleneglycol (540g) and catalyzer tetrabutyl titanate (1g) add after in flask successively, rapidly flask is heated up and make it reach 150 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 7h, temperature of reaction is set to 220 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 220 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 12h discharging, obtain poly terephthalic acid sebacic acid butanediol ester-poly(lactic acid) segmented copolymer, its number average mol weight is 18.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 510%, has had remarkable improvement than poly(lactic acid).
Embodiment 6
By hydroxyl-terminated polylactic acid (150g) two in embodiment 4.1, dimethyl terephthalate (DMT) (380g), Succinic anhydried (300g), butyleneglycol (530g) and tetrabutyl titanate (1g) add after in flask successively, flask is heated up and makes it reach 150 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 5h, temperature of reaction is set to 230 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 230 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 8h discharging, obtain poly terephthalic acid succinic acid-butanediol ester-poly(lactic acid) segmented copolymer, its number average mol weight is 19.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 500%, has had remarkable improvement than poly(lactic acid).
Embodiment 7
The reactor of 10L with two ventages cools through repeatedly vacuumizing filling with inert gas by 7.1, then when passing into nitrogen, add rac-Lactide (3000g), propylene glycol (152g) and tin protochloride (1g), reaction system is sealed, be placed in the oil bath being preheated to 120 DEG C, stir 14 hours, obtain white crystalline polymkeric substance, after reaction terminates, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain two hydroxyl-terminated polylactic acid, its number average mol weight is 1.4kg/mol;
7.2 by hydroxyl-terminated polylactic acid (140g) two in embodiment 7.1, terephthalic acid (340g), monomethyl succinate (390g), butyleneglycol (550g) and tetrabutyl titanate (2g) add after in flask successively, flask is heated up and makes it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 7h, temperature of reaction is set to 220 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 220 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 8h discharging, obtain poly terephthalic acid succinic acid-butanediol ester-poly(lactic acid) segmented copolymer, its number average mol weight is 15.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 260%, has had remarkable improvement than poly(lactic acid).
Embodiment 8
By hydroxyl-terminated polylactic acid (140g) two in embodiment 7.1, terephthalic acid (340g), dimethyl succinate (430g), butyleneglycol (600g) and tetrabutyl titanate (2g) add after in flask successively, flask is heated up and makes it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 6h, temperature of reaction is set to 230 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 230 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 7h discharging, obtain poly terephthalic acid succinic acid-butanediol ester-poly(lactic acid) segmented copolymer, its number average mol weight is 18.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 310%, has had remarkable improvement than poly(lactic acid).
Embodiment 9
By hydroxyl-terminated polylactic acid (140g) two in embodiment 7.1, dimethyl terephthalate (DMT) (190g), succinic acid dicyclohexyl ester (550g), butyleneglycol (400g) and tetrabutyl titanate (1g) add after in flask successively, flask is heated up and makes it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 6h, temperature of reaction is set to 220 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 220 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 10h discharging, obtain poly terephthalic acid succinic acid-butanediol ester-poly(lactic acid) segmented copolymer, its number average mol weight is 15.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 210%, has had remarkable improvement than poly(lactic acid).
Embodiment 10
By hydroxyl-terminated polylactic acid (140g) two in embodiment 7.1, dimethyl terephthalate (DMT) (390g), pyrovinic acid (400g), butyleneglycol (550g) and tetrabutyl titanate (1g) add after in flask successively, flask is heated up and makes it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 5h, temperature of reaction is set to 240 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 240 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 6h discharging, obtain poly terephthalic acid pyrovinic acid butanediol ester-poly(lactic acid) segmented copolymer, its number average mol weight is 16.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 330%, has had remarkable improvement than poly(lactic acid).
Embodiment 11
The reactor of 10L with two ventages cools through repeatedly vacuumizing filling with inert gas by 11.1, then when passing into nitrogen, add rac-Lactide (1500g), Diethylene Glycol (134g) and stannous octoate (1g), reaction system is sealed, put in the oil bath being preheated to 120 DEG C, stir 24 hours, obtain transparent polymkeric substance, after reaction terminates, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain two hydroxyl-terminated polylactic acid, its number average mol weight is 1.4kg/mol;
Two in embodiment 11.1 hydroxyl-terminated polylactic acid (160g), naphthalene dicarboxylic anhydride (80g), succinic acid (480g), butyleneglycol (450g) and tetrabutyl titanate (2g) are added after in flask successively, flask is heated up and makes it reach 200 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 4h, temperature of reaction is set to 260 degrees Celsius, progressively raise the temperature of system, when reaching 260 degrees Celsius, vacuumize polycondensation.Decompression step by step, to high vacuum state, carries out polycondensation, 6h discharging, obtains poly-naphthalic acid succinic acid-butanediol ester-poly(lactic acid) segmented copolymer, and its number average mol weight is 15.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 210%, has had remarkable improvement than poly(lactic acid).
Embodiment 12
By hydroxyl-terminated polylactic acid (160g) two in embodiment 11.1, m-phthalic acid (100g), hexanodioic acid (470g), butyleneglycol (400g) and tetrabutyl titanate (1g) add after in flask successively, rapidly flask is heated up and make it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 5h, temperature of reaction is set to 250 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 250 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 6h discharging, obtain poly-m-phthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer, its number average mol weight is 18.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 260%, has had remarkable improvement than poly(lactic acid).
Embodiment 13
By hydroxyl-terminated polylactic acid (160g) two in embodiment 11.1, 4, 4-phenylate dioctyl phthalate (70g), succinic acid (480g), ethylene glycol (400g) and tetrabutyl titanate (1g) add after in flask successively, flask is heated up and makes it reach 230 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 4h, temperature of reaction is set to 290 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 290 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 4h discharging, obtain polyphenylene oxide dioctyl phthalate EGS ethylene glycol succinate-poly(lactic acid) segmented copolymer, its number average mol weight is 15.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 240%, has had remarkable improvement than poly(lactic acid).
Embodiment 14
The reactor of 10L with two ventages cools through repeatedly vacuumizing filling with inert gas by 14.1, then when passing into nitrogen, add rac-Lactide (1500g), propylene glycol (110g) and stannous octoate (1g), reaction system is sealed, is placed in the oil bath being preheated to 180 DEG C, stir 9 hours, obtain transparent polymkeric substance, after reaction terminates, vacuumize and remove unreacted monomer, obtain two hydroxyl-terminated polylactic acid, its number average mol weight is 1kg/mol;
14.2 by hydroxyl-terminated polylactic acid (160g) two in embodiment 14.1, dimethyl terephthalate (DMT) (380g), hexanodioic acid (560g), ethylene glycol (450g) and tetrabutyl titanate (2g) add after in flask successively, flask is heated up and makes it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 5h, temperature of reaction is set to 225 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 225 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 8h discharging, obtain poly terephthalic acid ethylene glycol adipate(EGA)-poly(lactic acid) segmented copolymer, its number average mol weight is 19.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 320%, has had remarkable improvement than poly(lactic acid).
Embodiment 15
By hydroxyl-terminated polylactic acid (100g) two in embodiment 14.1, terephthalic acid (380g), hexanodioic acid (550g), 1, 3-hexylene glycol (850g) and tetrabutyl titanate (2g) add after in flask successively, flask is heated up and makes it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 6h, temperature of reaction is set to 230 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 230 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 7h discharging, obtain poly terephthalic acid hexanodioic acid hexylene glycol ester-poly(lactic acid) segmented copolymer, its number average mol weight is 17.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 330%, has had remarkable improvement than poly(lactic acid).
Embodiment 16
By hydroxyl-terminated polylactic acid (100g) two in embodiment 14.1, terephthalic acid (190g), hexanodioic acid (550g), 1, 4-cyclohexanediol (750g) and tetrabutyl titanate (1g) add after in flask successively, flask is heated up and makes it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 6h, temperature of reaction is set to 250 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 250 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 5h discharging, obtain poly terephthalic acid hexanodioic acid cyclohexanediol ester-poly(lactic acid) segmented copolymer, its number average mol weight is 17.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 310%, has had remarkable improvement than poly(lactic acid).
Embodiment 17
By hydroxyl-terminated polylactic acid (100g) two in embodiment 14.1, dimethyl terephthalate (DMT) (380g), hexanodioic acid (560g), one contracting propylene glycol (900g) and tetrabutyl titanate (2g) add after in flask successively, flask is heated up and makes it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 5h, temperature of reaction is set to 260 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 260 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 4h discharging, obtain poly terephthalic acid hexanodioic acid one contracting propylene glycol ester-poly(lactic acid) segmented copolymer, its number average mol weight is 16.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 280%, has had remarkable improvement than poly(lactic acid).
Embodiment 18
By hydroxy-end capped poly(lactic acid) (150g) two in embodiment 14.1, terephthalic acid (370g), hexanodioic acid (560g), Diethylene Glycol (750g) and tetrabutyl titanate (1g) add after in flask successively, flask is heated up and makes it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 5h, temperature of reaction is set to 250 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 250 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 6h discharging, obtain poly terephthalic acid hexanodioic acid binaryglycol ester-poly(lactic acid) segmented copolymer, its number average mol weight is 18.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 410%, has had remarkable improvement than poly(lactic acid).
Embodiment 19
The reactor of 10L with two ventages cools through repeatedly vacuumizing filling with inert gas by 19.1, then when passing into nitrogen, adds rac-Lactide (1500g), Isosorbide-5-Nitrae cyclohexanediol (116g) and stannous octoate (1g).Reaction system is sealed, is placed in the oil bath being preheated to 140 DEG C, stirs 20 hours, obtain white crystalline polymkeric substance, after reaction terminates, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain two hydroxyl-terminated polylactic acid, its number average mol weight is 1.5kg/mol.
19.2 by hydroxyl-terminated polylactic acid (100g) two in embodiment 19.1, terephthalic acid (370g), hexanodioic acid (700g), butyleneglycol (750g) and tin protochloride (1g) add after in flask successively, flask is heated up and makes it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 5h, temperature of reaction is set to 220 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 220 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 12h discharging, obtain poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer, its number average mol weight is 15.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 320%, has had remarkable improvement than poly(lactic acid).
Embodiment 20
By hydroxyl-terminated polylactic acid (100g) two in embodiment 19.1, terephthalic acid (370g), hexanodioic acid (700g), butyleneglycol (750g) and zinc acetate (1g) add after in flask successively, flask is heated up and makes it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 5h, temperature of reaction is set to 240 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 240 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 6h discharging, obtain poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer, its number average mol weight is 17.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 350%, has had remarkable improvement than poly(lactic acid).
Embodiment 21
By hydroxyl-terminated polylactic acid (100g) two in embodiment 19.1, terephthalic acid (370g), hexanodioic acid (700g), butyleneglycol (750g) and tosic acid (1g), tin protochloride (1g) adds after in flask successively, flask is heated up and makes it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 5h, temperature of reaction is set to 270 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 270 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 6h discharging, obtain poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer, its number average mol weight is 20.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 600%, has had remarkable improvement than poly(lactic acid).
Embodiment 22
By hydroxyl-terminated polylactic acid (100g) two in embodiment 19.1, terephthalic acid (370g), hexanodioic acid (700g), butyleneglycol (750g) and stannous octoate (1g) add after in flask successively, flask is heated up and makes it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 5h, temperature of reaction is set to 230 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 230 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 7h discharging, obtain poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer, its number average mol weight is 15.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 280%, has had remarkable improvement than poly(lactic acid).
Embodiment 23
The reactor of 10L with two ventages cools through repeatedly vacuumizing filling with inert gas by 23.1, then when passing into nitrogen, add rac-Lactide (1500g), 1,4 cyclohexanediols (116g) and stannous octoate (1g), reaction system is sealed, be placed in the oil bath being preheated to 140 DEG C, stir 20 hours, after reaction terminates, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain two hydroxyl-terminated polylactic acid, its number average mol weight is 1.4kg/mol;
23.2 by hydroxyl-terminated polylactic acid (150g) two in embodiment 23.1, dimethyl terephthalate (DMT) (380g), dimethyl succinate (700g), butyleneglycol (750g) and stannous octoate (1g) add after in flask successively, flask is heated up and makes it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 5h, temperature of reaction is set to 250 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 250 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, discharging after 7h, obtain poly terephthalic acid succinic acid-butanediol ester-poly(lactic acid) segmented copolymer, its number average mol weight is 18.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 380%, has had remarkable improvement than poly(lactic acid).
Embodiment 24
By hydroxyl-terminated polylactic acid (100g) two in embodiment 23.1, terephthalic acid (170g), sebacic acid (400g), decanediol (600g) and stannous octoate (1g) add after in flask successively, flask is heated up and makes it reach 230 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 5h, temperature of reaction is set to 260 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 260 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, discharging after 5h, obtain poly terephthalic acid sebacic acid decanediol ester-poly(lactic acid) segmented copolymer, its number average mol weight is 15.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 310%, has had remarkable improvement than poly(lactic acid).
Embodiment 25
Two in embodiment 23.1 hydroxyl-terminated polylactic acid (150g), terephthalic acid (370g), hexanodioic acid (700g), butyleneglycol (750g) and stannous octoate (1g) are added after in flask successively, rapidly flask is heated up and make it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 5h, temperature of reaction is set to 220 degrees Celsius, progressively raise the temperature of system, when reaching 220 degrees Celsius, vacuumize polycondensation.Decompression step by step, to high vacuum state, carries out polycondensation, 20h discharging, obtains poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer, and its number average mol weight is 16.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 290%, has had remarkable improvement than poly(lactic acid).
Embodiment 26
The reactor of 10L with two ventages cools through repeatedly vacuumizing filling with inert gas by 26.1, then when passing into nitrogen, adds rac-Lactide (1500g), propylene glycol (116g) and stannous octoate (1g); Reaction system sealed, be placed in the oil bath being preheated to 140 DEG C, stir 20 hours, after reaction terminates, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain two hydroxyl-terminated polylactic acid, its number average mol weight is 1.5kg/mol;
26.2 by hydroxyl-terminated polylactic acid (150g) two in embodiment 26.1, terephthalic acid (370g), hexanodioic acid (700g), butyleneglycol (750g) and stannous octoate (10g) add after in flask successively, flask is heated up and makes it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 5h, temperature of reaction is set to 240 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 240 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 5h discharging, obtain poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer, its number average mol weight is 17.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 310%, has had remarkable improvement than poly(lactic acid).
Embodiment 27
By hydroxyl-terminated polylactic acid (150g) two in embodiment 26.1, terephthalic acid (370g), hexanodioic acid (700g), butyleneglycol (750g) and stannous octoate (0.1g) add after in flask successively, flask is heated up and makes it reach 160 degrees Celsius and stir reactant, collect the water that reaction generates simultaneously, after 5h, temperature of reaction is set to 270 degrees Celsius, progressively raise the temperature of system, polycondensation is vacuumized when reaching 270 degrees Celsius, decompression step by step is to high vacuum state, carry out polycondensation, 6h discharging, obtain poly terephthalic acid tetramethylene adipate-poly(lactic acid) segmented copolymer, its number average mol weight is 15.0kg/mol.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the segmented copolymer that the present embodiment obtains is 350%, has had remarkable improvement than poly(lactic acid).
As seen from the above embodiment, the invention provides a kind of aliphatic-aromatic-poly(lactic acid) segmented copolymer, obtained by following preparation method: two hydroxyl-terminated polylactic acid, aromatic binary carboxylic acid compounds, aliphatic dicarboxylic acid compounds and dibastic alcohol compound are carried out esterification and polycondensation, obtain aliphatic-aromatic-poly(lactic acid) segmented copolymer.Aliphatic-aromatic provided by the invention-poly(lactic acid) segmented copolymer comprises aliphatic-aromatic segment, improves the snappiness of aliphatic-aromatic-poly(lactic acid) segmented copolymer.Experimental result shows: the elongation at break of aliphatic-aromatic provided by the invention-poly(lactic acid) segmented copolymer is 210% ~ 600%.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. aliphatic-aromatic-poly(lactic acid) segmented copolymer, is obtained by following preparation method:
Two hydroxyl-terminated polylactic acid, aromatic binary carboxylic acid compounds, aliphatic dicarboxylic acid compounds and dibastic alcohol compound are carried out esterification and polycondensation, obtains aliphatic-aromatic-poly(lactic acid) segmented copolymer.
2. aliphatic-aromatic according to claim 1-poly(lactic acid) segmented copolymer, is characterized in that, the number average mol weight of described pair of hydroxyl-terminated polylactic acid is 0.9kg/mol ~ 7.5kg/mol.
3. aliphatic-aromatic according to claim 1-poly(lactic acid) segmented copolymer, it is characterized in that, described aromatic binary carboxylic acid compounds comprise in the two alkyl ester of phthalic acid, naphthalic acid, phenylate dioctyl phthalate, aromatic diacid acid anhydride, aromatic binary carboxylic acid mono alkyl ester and aromatic binary carboxylic acid one or more.
4. aliphatic-aromatic according to claim 1-poly(lactic acid) segmented copolymer, is characterized in that, described dibastic alcohol compound is one or more in the dibastic alcohol compound of C2 ~ C50;
Described aliphatic dicarboxylic acid compounds is one or more in the aliphatic dicarboxylic acid compounds of C2 ~ C40.
5. aliphatic-aromatic according to claim 1-poly(lactic acid) segmented copolymer, is characterized in that, the temperature of described esterification is 150 DEG C ~ 230 DEG C;
The time of described esterification is 1h ~ 10h.
6. aliphatic-aromatic according to claim 1-poly(lactic acid) segmented copolymer, is characterized in that, the temperature of described polycondensation is 210 DEG C ~ 280 DEG C;
The time of described polycondensation is preferably 2h ~ 48h;
The pressure of described polycondensation is 50Pa ~ 2000Pa.
7. aliphatic-aromatic according to claim 1-poly(lactic acid) segmented copolymer, it is characterized in that, total amount of substance of described aliphatic dicarboxylic acid compounds and aromatic binary carboxylic acid compounds is 1:1 ~ 1:2 with total amount of substance ratio of described dibastic alcohol compound and two hydroxyl-terminated polylactic acid;
The amount of substance of described aromatic binary carboxylic acid compounds and described aliphatic dicarboxylic acid compounds is than being 10:90 ~ 90:10;
Described dibastic alcohol compound is 10:90 ~ 90:10 with the amount of substance ratio of described pair of hydroxyl-terminated polylactic acid.
8. aliphatic-aromatic described in claim 1 ~ 7 any one-poly(lactic acid) segmented copolymer, has structure shown in formula I:
In formula I, described R
1be selected from alkylene or-R
5-O-R
6, described R
5and R
6independently selected from alkylene;
Described R
2be selected from alkylene;
Described R
3be selected from alkylene or-R
7-O-R
8, described R
7and R
8independently selected from alkylene;
Described R
4be selected from aromatic base or-R
9-O-R
10, described R
9and R
10independently selected from aromatic base;
Described m=6 ~ 50, n=5 ~ 500, p=1 ~ 50, q=1 ~ 50, s=5 ~ 500.
9. aliphatic-aromatic-poly(lactic acid) segmented copolymer according to claim 8, is characterized in that, described m=10 ~ 40, n=50 ~ 400, p=10 ~ 40, q=10 ~ 40, s=50 ~ 400.
10. aliphatic-aromatic-poly(lactic acid) segmented copolymer according to claim 8, is characterized in that, described R
1be selected from alkylene or the-R of C2 ~ C50
5-O-R
6, described R
5and R
6independently selected from C2 ~ C25 alkylene;
Described R
2be selected from the alkylene of C2 ~ C40;
Described R
3be selected from alkylene or the-R of C2 ~ C50
7-O-R
8, described R
7and R
8independently selected from C2 ~ C25 alkylene.
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| CN109762143A (en) * | 2019-01-29 | 2019-05-17 | 中国科学院理化技术研究所 | Hydrolyzable copolyesters and its preparation method and application |
| CN112062939A (en) * | 2020-09-15 | 2020-12-11 | 常州大学 | High-resilience polylactic acid block copolymer and preparation method thereof |
| CN113956486A (en) * | 2021-11-11 | 2022-01-21 | 中国科学院长春应用化学研究所 | Long-chain branched polylactic acid-based copolymer and preparation method thereof |
| WO2022213498A1 (en) * | 2021-04-08 | 2022-10-13 | 苏州楷儒新材料科技有限公司 | Preparation method for biodegradable polyester chip |
| CN115260478A (en) * | 2022-07-19 | 2022-11-01 | 绍兴文理学院 | Preparation method and application of high-strength high-toughness polylactic acid copolymer |
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| CN115260478A (en) * | 2022-07-19 | 2022-11-01 | 绍兴文理学院 | Preparation method and application of high-strength high-toughness polylactic acid copolymer |
| CN115260478B (en) * | 2022-07-19 | 2024-02-02 | 绍兴文理学院 | Preparation method and application of high-strength high-toughness polylactic acid copolymer |
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